Method for generation of memory effects on hair

ABSTRACT

Disclosed is a method for achieving a recallable hair deformation. A composition is applied onto hair, comprising at least one active agent, which, alone or in combination with further compounds, is able, after application to the hair and after carrying out the treatment of hair in accordance with the present invention, to provide a shape memory effect. The hair is brought into a defined (permanent) shape and the permanent shape is subsequently fixed by means of inducing a chemical or physical change of the applied agents, wherein after a desired or undesired deformation, the memory shape of the initial memory shape may be recovered by means of a physical stimulation. Suitable active agents are for example macromers which may be cross-linked to provide shape memory polymers, wherein the permanent shape is fixed by means of the chemical cross-linking of the macromer, providing a shape memory polymer, which possesses at least one transition temperature T trans . Suitable active agents are also shape memory polymers, which have hard segments which may be cross-linked by physical interactions having a first transition temperature T′ trans , which preferably is at least 10° C. above room temperature, and soft segments having a second transition temperature which preferably is at least 10° C. below T′ trans . In addition to the permanent hairdo, a second (temporary) shape can be impressed. Furthermore, disclosed is a method for the recovery of a once programmed permanent hairdo, which has been brought into a temporary shape or which has been deformed in any other way.

The present invention concerns a method of providing a recallable hairshape transformation using active agents, which provide hair with ashape-memory effect, in particular macromers which are cross-linkable toshape memory polymers or shape memory polymers.

In the field of shaping of hair, a distinction is usually made betweentemporary hair-shaping methods and long-lasting, permanent hair-shapingmethods. A temporary hair-shaping usually occurs in connection with theuse of compositions on the basis of solutions or dispersions comprisinghair-fixative polymers. Such products provide the hair, by means of thepolymers used, with improved hold, volume, elasticity, body and shine.Such styling products facilitate, for example, in the form of a gel, theshaping and provision of a hairdo; they improve, in the form of hairspray, the condition of a prepared hairdo; and they increase, in theform of setting foams, the volume of the hair. A drawback in thisconnection is that the desired effects are of only relatively shortduration, and that they are lost under external influences, such ascombing, wind, high humidity, or contact with water. A permanent hairtransformation usually occurs during a treatment of providing apermanent wave. During this treatment the disulfide bonds in the hairare cleaved by use of a reductive reaction, the hair is brought into thenew shape, and this new shape is fixed by

The present invention concerns a method of providing a recallable hairshape transformation using active agents, which provide hair with ashape-memory effect, in particular macromers which are cross-linkable toshape memory polymers or shape memory polymers.

In the field of shaping of hair, a distinction is usually made betweentemporary hair-shaping methods and long-lasting, permanent hair-shapingmethods. A temporary hair-shaping usually occurs in connection with theuse of compositions on the basis of solutions or dispersions comprisinghair-fixative polymers. Such products provide the hair, by means of thepolymers used, with improved hold, volume, elasticity, body and shine.Such styling products facilitate, for example, in the form of a gel, theshaping and provision of a hairdo; they improve, in the form of hairspray, the condition of a prepared hairdo; and they increase, in theform of setting foams, the volume of the hair. A drawback in thisconnection is that the desired effects are of only relatively shortduration, and that they are lost under external influences, such ascombing, wind, high humidity, or contact with water. A permanent hairtransformation usually occurs during a treatment of providing apermanent wave. During this treatment the disulfide bonds in the hairare cleaved by use of a reductive reaction, the hair is brought into thenew shape, and this new shape is fixed by providing new disulfide bondsby means of an oxidative process. A drawback in this respect, however,is that the required chemical treatment of the hair employing reductionagents and oxidation agents involves an impairment of the structure ofthe hair. A further drawback of the methods for hair shaping known up tonow is that it is not possible to revert a once-performed transformation(shaping) using relatively simple means, i.e., it is not possible tochange from one shape of a hairdo to another shape of a hairdo withouttroublesome processes. JP 04-41416 discloses compositions in the fieldof cosmetic preparations for hair which comprise specific linearpolyurethanes having a glass transition temperature T_(g) of from 40 to90° C. The process for hair treatment disclosed therein corresponds tothe treatment using conventional thermoplastic materials. After theadministration of the composition, a hairdo is prepared at a temperatureabove T_(g), and this hairdo is then fixed by means of cooling underT_(g). During a subsequent rewarming to a temperature above Tg, thepolymer softens and a new hairdo can be prepared. A method for arecallable, reversible hair-shaping (hair transformation), however, isnot disclosed. The properties of the linear polyurethanes are notsatisfactory in order to provide a recallable hair shaping.

The object underlying the present invention was to provide a method andthe therefore required products for providing a recallable hairtransformation (hair-shaping) enabling a high degree of recovery of aonce-programmed hairdo. A further object was to provide a methodenabling a permanent hair-shaping without requiring an impairingintervention into the hair structure. A further object was the provisionof a method which enables the reversion of a temporarytransformation/shaping over multiple cycles with a high accuracy inorder to revert to a previously prepared, programmed permanent hairdo. Afurther object was also the provision of a method which enables in asimple manner to remedy with a high accuracy the deformation of a hairdowhich has been introduced by external influences, in order to revert toa once prepared, programmed permanent hairdo.

This object has been solved with a method for treating hair, comprising:

applying onto the hair a composition which comprises at least one activeagent, select among compounds which, alone or in combination withfurther compounds, is capable, after application to hair and afterhaving carried out the treatment defined in the following, to provide ashape memory effect to hairs,

previously, at the same time or subsequently bringing the hair into adesired shape (permanent memory shape), and

subsequently fixing the memory shape by inducing a physical or chemicalchange of the applied active agents,

wherein after a desired or undesired deformation of the memory shape theinitial memory shape can be recovered substantially by means of aphysical stimulation.

A preferred embodiment concerns a method for hair treatment, comprisingthe steps of

applying a composition, which comprises at least one crosslinkablemacromer, which forms after crosslinking a shape-memory polymer, ontothe hair, wherein the macromer

-   -   a. comprises crosslinkable areas (segments) which are        crosslinkable by means of chemical bonds and    -   b. thermoplastic areas (segments) which are not chemically        crosslinkable,    -   bringing the hair, previously, at the same time or subsequently,        into a desired (permanent) shape and    -   fixing the shape by means of chemical crosslinking of the        macromer, thereby providing the shape memory polymer,

characterized in that the shape memory polymer possesses at least onetransition temperature T_(trans).

A further object of the present invention is a method for impressing asecond hairdo over a programmed, recallable first hairdo. In thismethod, a hairdo, programmed by means of the above-explained method(permanent shape) is heated to a temperature above T_(trans).Subsequently, the hair is brought into the second (temporary) shape andthe second shape is fixed by means of cooling to a temperature belowT_(trans).

A further subject of the present invention is a method for the recoveryof a first hairdo, programmed by means of the above-explained method(permanent shape). Therein, a hairdo in a temporary shape or in theshape of a hairdo obtained by means of cold forming, is heated to atemperature above T_(trans).

Shape-memory polymers in accordance with the present invention arepolymers from which materials can be prepared which possess the propertythat they can be impressed with a desired shape (permanent shape), towhich these materials, after deformation or after impressing a secondshape (temporary shape), can revert spontaneously and without externalforces by means of simple warming or by means of another energeticstimulus. Deformation and retransformation (recovery) can be carried outover multiple cycles. The degree of attainability of the initial,permanent shape, is during a first relaxation cycle consisting ofdeformation and recovery, usually somewhat smaller than during thesubsequent cycles, most probably due to the removal of existingtextures, defects, etc., initially present. A very high degree ofrecovery will, however, be attained during the subsequent relaxationcycles. The degree of recovery during the first relaxation cycle ispreferably at least 30%, in particular at least 50% and the degree ofrecovery during the subsequent relaxation cycles is preferably at least60%, more preferably at least 80%. This degree may, however, be also 90%or more. The degree of recovery can be measured in accordance with usualcurl-retention measurements by means of the determination of the lengthof a treated hair strand or by means of known, suitable stress-strainexperiments.

The shape memory effect on hair is the property the a specific hairdo(permanent memory shape) may be substatially recalled, after adeformation, spontaneously and without the application of any externalforces by simple heating or some other energetic stimulus, i.e. to adegree during the first recovery cycle of at least 30%, preferably atleast 50%, and to a degree, during subsequent cycles of recovery of atleast 60%, preferably at least 80% or 90%.

Macromers or pre-polymers in accordance with the present invention whichcan be crosslinked in order to provide shape-memory polymers, arepolymers or oligomers wherein the fixation of an impressed, permanentshape occurs by means of chemical bonds connecting specific polymerstrands or oligomer strands. The crosslinkage, by means of chemicalbonds, can be provided by means of ionic or covalent bonds. Thecrosslinking reaction may be any suitable chemical reaction, forexample, a salt formation reaction, a condensation reaction, an additionreaction, a substitution reaction or a reaction initiatedphotochemically or by means of a radical. The crosslinking reaction canoccur using suitable catalysts or initiators or the crosslinkingreaction can occur without the use of a catalyst. The crosslinkingreaction can be initiated by means of a suitable energy source, forexample, electromagnetic radiation, ultrasound, heat or mechanicalenergy. A combination of two or more methods for initiation can beemployed in order to increase the efficiency or the velocity of thecrosslinking reaction.

Shape-memory polymers which can be used in accordance with the presentinvention possess at least one transition temperature T_(trans). Thistransition temperature may be a melting temperature T_(m) or a glasstransition temperature T_(g). Above T_(trans), the polymer has a lowermodulus of elasticity than below T_(trans). The ratio of the modulus ofelasticity below T_(trans) to above T_(trans) is preferably at least 20.The transition temperature T_(trans) is preferably above roomtemperature (20° C.), preferably this transition temperature is at least30° C., in particular preferred 40° C. The transition temperatureT_(trans) is the temperature above which the spontaneous recovery of thepermanent shape, starting from the deformed shape or the temporaryshape, occurs.

The terms “hairdos” or “shape of hair” in accordance with the presentinvention are to be understood broadly and comprise in particular alsothe degree of waviness or the degree of evenness of hair. A programmedhairdo in accordance with the present invention is any group of hairswhich show a specific shape due to shape-memory polymers which have beencrosslinked and which fix a permanent shape. Recovery of a programmedhairdo in accordance with present invention means that the programmedhairdo is recovered after a deformation, to a degree of at least 60%,preferably to a degree of at least 80%, in relation to the shape whichcan be obtained after a first relaxation cycle. The degree of recoverycan, for example, be determined by means of the determination of thelength of a hair strand or hair curl.

Suitable macromers or pre-polymers, which can be chemically crosslinkedin order to provide shape-memory polymers are macromonomers which can bepolymerized or which can be crosslinked by means of single chemicalbonds. The chemically crosslinkable polymers are designated as thermosetpolymers in WO 99/42147. The macromers and thermoset polymers disclosedin WO 99/42147 are suitable for use in accordance with the presentinvention and these materials are incorporated here by reference. Soft,thermoplastic segments (switching segments) having a transitiontemperature T_(trans) are crosslinked by means of chemical, preferablycovalent bonds. Required are switching segments and fixation points(network points). The fixation points fix the permanent form while theswitching segments fix the temporary shape. The shape memory effect isbased on the change of the elasticity at, above, or below T_(trans) orduring the transition from above to below T_(trans) or from below toabove T_(trans). The ratio of the modulus of elasticity below T_(trans)to above T_(trans) is preferably at least 20. The higher this ratio is,the more expressed the shape-memory effect can be obtained. Four typesof thermoset polymers having shape-memory properties can be designated:

Network polymers, penetrating network polymers, semi-interpenetratingnetworks and mixed penetrating networks. Network polymers can be formedby means of the covalent connection of macromonomers, i.e., of oligomersor polymers having reactive terminal groups, preferably ethylenicallyunsaturated terminal groups, terminal groups which can be reacted bymeans of radical reactions or terminal groups which can be reacted bymeans of photochemical reactions. The crosslinking reaction can, forexample, be initiated by means of light-sensitive ortemperature-sensitive initiators, by means of red-ox systems orcombinations thereof, or the reaction can be initiated without the useof initiators, e.g., using UV light, heat or mechanical energy.Interpenetrating networks are formed at least two components which areeach crosslinked but not with the other component. Mixedinterpenetrating networks are formed using at least two components,wherein one component is crosslinked by means of chemical bonds and thesecond component is crosslinked by means of physical interactions.Semi-interpenetrating networks are formed using at least two components,of which one is chemically crosslinkable, while the other one is notchemically crosslinkable. Both components, however, cannot be separatedfrom one another by means of physical methods.

In principle, all synthetic or natural oligomers or polymers havingreactive terminal groups or side chain groups, which provide thecrosslinked shape-memory polymer with a suitable transition temperatureT_(trans) and suitable moduli of elasticity above and below T_(trans)are suitable, wherein the terminal groups or the side chain groups arealready present initially or are provided by means of a subsequentderivatization. These materials allow a crosslinking reaction using theabove-identified methods. Suitable macromers are, for example, macromershaving the following formulaA1-(X)_(n)-A2   (I)

wherein A1 and A2 designate reactive, chemically crosslinkable groupsand wherein

—(X)n- designates a divalent, thermoplastic polymer or oligomersegement. A1 and A2 are preferably acrylate or methacrylate groups. Thesegment —(X)n- preferably designates a polyester segment, an oligoestersegment, a polyalkylene glycol segment, an oligoalkylene glycol segment,a polyalkylene carbonate segment or a oligoalkylene carbonate segment,wherein the alkylene groups are preferably ethylene groups or propylenegroups. Suitable macromonomers for the formation of thermoset polymershaving shape-memory properties are oligo-(ε-caprolactone) orpoly(ε-caprolactone), oligolactide or polylactide, oligoalkylene glycol,polyalkyleneglycol, e.g., polyethylene glycol or their block copolymers,wherein the polymers or oligomers possess at least two ethylenicallyunsaturated groups, which can be polymerized by means of a radicalreaction, e.g., acrylates or methacrylates, wherein these groups areprovided at a terminal position or at any side chain position.

The polymer segments can be chosen among natural polymers, such as, forexample, segments derived from proteins or polysaccharides. Suitable arealso synthetic polymer segments. Suitable natural polymer segments areproteins such as zein, modified zein, casein, gelatine, gluten, serumalbumin or collagen, as well as polysaccharides such as alginate,cellulose, dextrane, pullulane or polyhyaluronic acid, as well aschitin, poly(3-hydroxyalkanoate), especially poly(β-hydroxybutyrate),poly(3-hydroxyoctanoate) or poly(3-hydroxyfatty acids). Suitable arealso derivatives of natural polymer segments such as alkylated,hydroxyalkylated, hydroxylated or oxidated modifications.

Synthetically modified natural polymers are, for example, cellulosederivatives such as alkylcelluloses, hydroxyalkylcelluloses, celluloseethers, cellulose esters, nitrocellulose, chitosan or chitosanderivatives, which are, e.g., obtained by means of alkyl substitution orhydroxyalkyl substitution at the nitrogen and/or oxygen. Examples aremethylcellulose, ethylcellulose, hydroxypropylcellulose,hydroxypropylmethylcellulose, hydroxybutylmethylcellulose,celluloseacetate, cellulosepropionate, celluloseacetatebutyrate,celluloseacetatephthalate, carboxymethylcellulose, cellulosetriacetateor cellulosesulfate sodium salt. These materials are all designated inthe following as “celluloses.”

Suitable synthetic polymer blocks include polyphosphazenes,poly(vinylalcohols), polyamides, polyesteramides, poly(aminoacids),polyanhydrides, polycarbonates, polyacrylates, polyalkylenes,polyacrylamides, polyalkylenglycoles, polyalkylenoxides,polyalkylenterephthalates, polyorthoesters, polyvinylethers,polyvinylesters, polyvinylhalogenides, polyvinylpyrrolidones,polyesters, polylactide, polyglycolide, polysiloxanes, polyurethanes andcopolymers thereof. Examples of suitable polyacrylate arepoly(methylmethacrylate), poly(ethylmethacrylate),poly(butylmethacrylate), poly(isobutylmethacrylate),poly(hexylmethacrylate), poly(isodecylmethacrylate),poly(laurylmethacrylate), poly(phenylmethacrylate),poly(methylacrylate), poly(isopropylacrylate), poly(isobutylacrylate) orpoly(octadecylacrylate). Suitable synthetic, biologically degradablepolymer segments are polyhydroxyacids such as polylactide, polyglycolideand and copolymers thereof, poly(ethylenterephthalate);poly(hydroxybuturic acid); poly(hydroxyvaleric acid);poly[lactide-co-(ε-caprolactone)]; poly[glycolide-co-(ε-caprolactone)];polycarbonates, poly(aminoacids); poly(hydroxyalkanoates);polyanhydrides; polyorthoesters as well as mixtures and copolymersthereof. Examples of polymer segments which are less readilybiologically degradable are poly(methacrylic acid), poly(acrylic acid),polyamides, polyethylene, polypropylene, polystyrene, polyvinylchloride,polyvinylphenol as well as mixtures and copolymers thereof.

In a prefer red embodiment of the present invention, the compositioncomprises a mixture of (A) macromers which are substituted with at leasttwo reactive, crosslinkable groups, and (B) macromers, which aresubstituted with only one reactive group. Suitable additional macromersare, for example, macromers of the following general formula:R—(X′)_(n)-A3   (II)

wherein R designates a monovalent organic residue, A3 designates areactive, chemically crosslinkable group and —(X′)_(n) designates adivalent, thermoplastic polymer segment or oligomer segment. A3preferably represents an acrylate group or a methacrylate group. Thesegment —(X′)_(n)— preferably represents a polyalkyleneglycol,monoalkylethers thereof, or block copolymers thereof, wherein thealkylene groups preferably are ethylene or propylene groups and whereinthe alkyl groups preferably comprise from 1 to 30 carbon atoms.

Particularly preferred are mixtures of (A) polyalkyleneglycoles orpolycaprolactones having terminal ester groups comprising acrylic acidor methacrylic acid and (B) polyalkyleneglycol-monoalkylethers, havingone terminal ester group comprising acrylic acid or methacrylic acidwherein the alkylene groups are preferably ethylene or propylene groupsand the alkyl groups are preferably C1-bis C30-alkyl groups.

As component (A) the following are, e.g., suitable:poly(ε-caprolactone)-dimethacrylate, poly(DL-lactide)-dimethacrylate,poly(L-lactide-co-glycolide)-dimethacrylate,poly(ethyleneglycol)dimethacrylate, poly(propyleneglycol)dimethacrylate,PEG-block-PPG-block-PEG-dimethacrylate,poly(ethyleneadipate)-dimethacrylate,hexamethylencarbonat-di-methacrylate.

Suitable as component (B) are, e.g., the following:poly-(ethyleneglycol)monoacrylate, poly(propyleneglycol)monoacrylate andmonoalkylethers thereof.

A further particular embodiment relates to a method of treating hair,comprising:

-   -   applying a composition onto hair, comprising at least one shape        memory polymer, which comprises at least two transition        temperatures T_(trans) and T′_(trans), and wherein this shape        memory polymer comprises at least one hard segment with a first        transition temperature T′_(trans), which is crosslinkable by        means of physical interactions, wherein the first transition        temperature is above room temperature, preferably more than        10° C. above room temperature, and at least one soft segment        having a second transition temperature T_(trans), which lies        below T′_(trans), preferably at least 10° C. below T′_(trans),    -   previously, at the same time or subsequently shaping the hair to        a defined (permanent) shape and, subsequently, fixing the shape        by means of a physical cross-linking of the shape memory        polymer.

The shaping of hair occurs suitably under warming to a temperature of atleast T′_(trans) and the shape of the hair is fixed by means of coolingto a temperature below T′_(trans). Room temperature in this connectionrefers generally to ambient temperature, preferably at least 20° C. and,in warmer climates, preferably at least 25° C. The application of thecomposition onto the hair can be carried out in different ways, forexample directly by spraying or in an indirect manner by applying thecomposition first to the hand or a suitable device, for example a comb,a brush etc, followed by a subsequent application within or onto thehair. The consistency of the composition may be the consistency of asolution, a dispersion, a lotion, a thickened lotion, a gel, a foam, asemi-solid composition, waxy or creamy.

A further embodiment of the invention is a method for impressing asecond hairdo over a programmed, recallable first hairdo. During thismethod the hairdo (permanent shape), programmed by means of theabove-mentioned method, is warmed to a temperature between T′_(trans)and T_(trans). Subsequently the hair is brought into the second(temporary) shape and this second shape is fixed by means of cooling toa temperature below T_(trans).

A further embodiment of the present invention is a method for recallinga programmed first hairdo (permanent shape), prepared by means of theabove-mentioned method. In this method the hairdo in a temporary shapeor in the shape of a hairdo being obtained by cold-forming, is warmed toa temperature above T_(trans). The permanent shape is formedspontaneously and without further external influence. Cold-forming of ahairdo is a change of the hairdo at ambient temperature, without the useof additional heating by means of a hairdryer or similar devices. Thedeformation can, for example, be carried out mechanically, for examplebe means of subjecting the curls to gravity, by means of combing orbrushing the hair, due to the influence of wind or humidity, due tomechanical influences during sleep or during lying.

The invention furthermore relates to a method for reprogramming apermanent hairdo, obtained with the above-mentioned method, into adifferent, new permanent shape. In order to achieve this goal, theinitial hairdo is warmed to a temperature above T′_(trans) and the hairis brought into a new shape. Subsequently this new form is fixed bymeans of cooling to a temperature below T′_(trans).

Shape memory polymers which may be crosslinked physically in accordancewith the present invention are polymers, with which the fixation of theimpressed permanent shape due to crosslinking occurs by physicalinteractions. A crosslinking by means of physical interactions can beachieved for example when specific segments of the polymer chains areassembled together in crystalline areas. The physical interactions maybe charge transfer complexes, hydrogen bonds, dipolar or hydrophobicinteractions, Van der Waals interactions or ionic interactions ofpolyelektrolyte segments. These interactions may occur between differentsegments within one polymer strand (intramolecular) and/or betweendifferent polymer strands (intermolecular). The formation of theinteractions may be initiated by means of cooling (in particular inrelation to crystallisation) and/or by means of drying, i.e. the removalof solvents.

Shape memory polymers which may be crosslinked physically and which aresuitable i n accordance with the present invention do show at least twotransition temperatures T_(trans) and T′_(trans). The two transitiontemperatures may for example be melting temperatures T_(m) or glasstransition temperatures T_(g). Above T_(trans) the polymer does show alower modulus of elasticity compared with the modulus of elasticitybelow T_(trans). The ratio of the moduli of elasticity below and aboveT_(trans) preferably is at least 10, more preferably at least 20. Thelower transition temperature T_(trans) preferably is higher than roomtemperature (20° C.), in particular at least 30° C., more preferably atleast 35° C. or at least 40° C. and this temperature is the temperatureat which the spontaneous recovery of the permanent shape from thedeformed or temporary shape occurs. T_(trans) is preferably above theusually to be expected ambient temperatures, so that at ambienttemperatures no significant, undesired, thermally induced deformation ofthe temporary hairdo occurs. Suitable ranges for T_(trans) are forexample from 25 to 100° C. , from 30 to 75° C., from 35 to 70° C. orfrom 40 to 60° C.

The upper transition temperature T′_(trans) is higher than T_(trans) andthis transition temperature is the temperature above which theimpression of the permanent shape or the reprogramming of a permanentshape into a new permanent shape occurs and below which the permanentshape is fixed. T′_(trans) preferably is to the extend higher thanT_(trans), so that during the warming of the hairdo to a temperatureabove T_(trans), for the recovery of the permanent shape or for thereforming of a temporary hairdo while maintaining the permanent shape,no significant, undesired, thermally induced deformation of thepermanent shape occurs. Preferably, T′_(trans) is at least 10° C., morepreferably at least 20° C. or at least 30° C. above T_(trans). Thedifference between T′_(trans) and T_(trans) may be for example from 10to 80° C., from 20 to 70° C. or from 30 to 60° C. Suitable ranges forT′_(trans) are for example from 40 to 150° C. from 50 to 100° C. or from70 to 95° C.

Suitable shape memory polymers which may be crosslinked physically arepolymers which consist of at least one hard segment and at least onesoft segment. The hard segment shows physical crosslinks and has atransition temperature T′_(trans) which is above room temperature,preferably more than 10° C. above 20° C. The soft segment has atransition temperature T_(trans) which is below T′_(trans), preferablyat least 10° C. below T′_(trans). The polymer segments are preferablyoligomers, in particular linear chain molecules having a molecularweight of for example 400 to 30,000 preferably 1,000 to 20,000 or 1,500to 15,000. These polymers may be linear di-block tri-block, tetra-blockor multi-block copolymers, they may be branched, dendritic or graftcopolymers. Preferably the se polymers are not linear polyurethanescomprising bis(2-hydroxy-ethyl)-hydroquinone. The molecular weight ofthe polymers may for example be from 30,000 to 1,000,000, preferablyfrom 50,000 to 700,000 or from 70,000 to 400,000. Suitable shape memorypolymers which may be crosslinked physically are disclosed in WO99/42147 and these polymers are disclosed there as thermoplasticpolymers. The thermoplastic polymers disclosed in WO 99/42147 as well asthe methods of preparation are suitable in accordance with the presentinvention and this disclosure is herewith incorporated by reference.These polymers do show a degree of crystallinity of preferably 3 to 80%,more preferably 3 to 60%. The ratio of the moduli of elasticity belowand above T_(trans) preferably is at least 10, more preferably at least20. The polymer segments may be segments derived from natural polymers,such as proteins or polysaccharides. The segments may also be syntheticpolymer blocks. Suitable natural or synthetic polymer segments areidentical with the crosslinkable macromers named above.

Suitable shape memory polymers are in particular multiblock copolymers,comprising at least one first type of blocks and at least one differentsecond type of blocks, wherein the blocks do enable that the multiblockcopolymer possesses two different transition temperatures. Suitablemultiblock copolymers are in particular copolymers prepared from atleast two different macrodiols and at least one diisocyanate. Macrodiolsare oligomers or polymers having at least two free hydroxyl groups.Oligomers do consist usually of at least two, preferably at least 3,more preferably 4 to 20, 5 to 15 or 6 to 10 monomers. The macrodiols maypossess the general formula HO—A—OH, wherein A defines a divalent,oligomeric or polymeric group, preferably a polyester or an oligoester.The diisocyanate may have the general formula OCN—B—NCO, wherein Bdefines a divalent organic group, preferably an alkylene group or anarylene group, which may be further substituted. The alkylene group maybe linear, branched or cyclic and this group preferably possesses 1 to30 carbon atoms, more preferably 2 to 20 or 5 to 15 carbon atoms.

Particularly preferred shape memory polymers are the copolyesterurethanes disclosed in WO 99/42147, in particular the reaction productsof (a) two different macrodiols, selected among α,ω-dihydroxypolyesters, α,ω-dihydroxy oligoesters, α,ω-dihydroxy polylactones andα,ω-dihydroxy oligolactones, and (b) at least one diisocyanate,preferably trimethylhexane-1,6-diisocyanate. In particular preferred aremacrodiols from poly(para-dioxanone) (PDX), poly(pentadecalactone)(PDL), poly(ε-caprolactone) (PCL), poly(L-lactide-co-glydolide) (PLGA).The molecular weights of the macrodiols are preferably within the rangeof from 400 to 30,000, preferable 1,000 to 20,000 or 1,500 to 15,000.The molecular weights of the resulting multiblock copolymers arepreferably M_(w) from 30,000 to 1,000,000, more preferably from 50,000to 70,000 or from 70,000 to 400,000 g/mol, as determined by GPC. Thepoly dispersity preferably is within the range of from 1.7 to 2.0.

One further preferred embodiment is concerned with a method for hairtreatment using a composition comprising at least two compounds, whichalone do show only minute or no shape memory properties but which, whenapplied in combination according to the method of the present inventionprovide the hair with a synergistically enhanced shape memory effect.

Compositions in accordance with present invention for the treatment ofhair comprise at least one of the above-mentioned macromers orpre-polymers, which is suitable to be crosslinked in order to provideshape-memory polymers, in an amount of preferably from 0.01 to 25 weight%, more preferably of from 0.1 to 15 weight % in a suitable liquidmedium. The composition can be provided in the form of a solution,dispersion, emulsion, suspension or latex. The liquid medium ispreferably cosmetically acceptable and physiologically acceptable.

The composition in accordance with present invention usually is presentin the form of a solution or dispersion comprising a suitable solvent.Preferred are in particular aqueous, alcoholic or aqueous-alcoholicsolvents. Suitable solvents are, e.g., aliphatic alcohols having from 1to 4 carbon atoms or a mixture of water with at least one of thesealcohols. Other organic solvents can, however, also be employed, inparticular linear or branched hydrocarbons, such as pentane, hexane,isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane,organic linear or cyclic ethers, such as tetrahydrofurane (THF) orliquid organic esters, such as ethylacetate. Furthermore, solvents onthe basis of silicone materials are suitable, in particular siliconeoils on the basis of linear or cyclic polydimethylsiloxanes (dimethiconeor Cyclomethicone). The solvents are preferably present in an amountfrom 0.5 to 99 weight %, more preferably in an amount from 40 to 90weight %.

The compositions in accordance with present invention may comprise inaddition from 0.01 to 25 weight % of at least one hair fixative, haircoloring agent and/or hair cosmetic. Hair fixatives are in particularthe known conventional film-forming hair fixative polymers. The filmforming and hair fixative polymer may be of synthetic origin or ofnatural origin and may be of nonionic, cationic, anionic or amphotericcharacter. Such a polymer additive, which can be present in an amount offrom 0.01 to 25 weight %, preferably 0.1 to 20 weight %, more preferably0.5 to 15 weight %, may also comprise a mixture of more than onepolymers, and this additive can be modified further with respect to thehair fixative properties by means of the addition of further polymershaving a thickening effect. Film-forming, hair fixative polymers inaccordance with present invention are polymers which are able, whenemployed in aqueous, alcoholic or aqueous-alcoholic solutions at aconcentration of from 0.01 to 5%, to provide a polymer film on the hairin order to provide fixative properties. As suitable, synthetic,nonionic, film-forming, hair fixative polymers, the hair treatmentcomposition in accordance with present invention may comprise homopolymers of vinyl pyrrolidone, homopolymers of N-vinylformamide,copolymers of vinylpyrrolidone and vinylacetate, terpolymers ofvinylpyrrolidone, vinylacetate and vinylpropionate, polyacrylamide,polyvinylalcohols, or polyethyleneglycols having a molecular weight offrom 800 to 20.000 g/mol. Suitable, synthetic, anionic, film-formingpolymers are crotonic acid/vinylacetate copolymers and terpolymers ofacrylic acid, ethylacrylate and N-t-butylacrylamide. Naturalfilm-forming polymers or polymers obtained therefrom by means ofchemical derivatization may also be employed in the hair treatmentcomposition in accordance with present invention. In this respect lowmolecular chitosane having a molecular weight of from 30,000 to 70,000g/mol or high molecular chitosane, derivatives of chitosane soluble inorganic solvents, mixtures of oligosaccharides, monosaccharides, anddisaccharides, China balsam resin, cellulose derivatives such ashydroxypropylcellulose having a molecular weight of from 30,000 to50,000 g/mol, or shellac in its neutralized or unneutralized form areknown as suitable. Amphoteric polymers can also be employed in the hairtreatment composition in accordance with present invention. Suitableare, e.g., copolymers of octylacrylamide, t-butylaminoethylmethacrylateand two or more monomers selected from the group consisting of acrylicacid, methacrylic acid and simple esters thereof.

Cationic polymers which can be used in accordance with present inventioncomprise copolymers of vinylpyrrolidones with quaternized derivatives ofdialkylaminoacrylate and dialkylaminomethacrylate, such as, for example,the copolymer of vinylpyrrolidone and dimethylaminomethacrylatequaternized with diethylsulfate. Further cationic polymers arecopolymers of vinylpyrrolidone with vinylimidazoliummethochloride, theterpolymer of dimethyldiallylammoniumchloride, sodiumacrylate andacrylamide, the terpolymer of vinylpyrrolidone,dimethyl-aminoethylmethacrylate and vinylcarprolactam, the quaternizedammonium salt, prepared from hydroxyethylcellulose and atrimethylammonium substituted epoxide, the vinylpyrrolidone andmethacrylamidopropyltrimethylammoniumchloride and diquaternizedpolydimethylsiloxanes.

The consistency of hair treatment compositions in accordance withpresent invention can be improved by means of the addition ofthickeners. In this respect, homopolymers of acrylic acid having amolecular weight of 2,000,000 to 6,000,000 g/mol are suitable. Furthercopolymers of acrylic acid and acrylamide (sodium salt) having amolecular weight of from 2,000,000 to 6,000,000 g/mol, sclerotium gumand copolymers of acrylic acid and methacrylic acid are suitable.

A cosmetic composition in accordance with present invention can beemployed in the form of different formulations for different types ofapplications, e.g., as lotion, as spray lotion, as cream, as gel, asfoam-gel, as aerosol spray, as non-aerosol spray, as aerosol foam, asnon-aerosol foam, as o/w- or w/o-emulsion, as micro emulsion or as hairwax.

When the hair treatment composition in accordance with present inventionis provided in the form of an aerosol spray, the composition comprisesadditionally from 15 to 85 weight %, preferably from 25 to 75 weight %of a propellant and the composition is filled into a pressurizedcanister having a spray button As propellants, lower alkanes, suchas-n-butane, isobutene and propane as well as mixtures thereof as wellas dimethylether or fluorohydrocarbons, such as F 152a(1,1-difluorethane) or F 134 (tetrafluorethane) are suitable, as well aspropellants which are present at the pressures in question in gaseousforms such as N₂, N₂O and CO₂ as well as mixtures of the above-mentionedpropellants.

When the hair treatment composition of the present invention is providedin the form of a sprayable non-aerosol hair spray, the composition issprayed by means of a suitable, mechanical spraying device. Spraydevices of the mechanical type are devices which allow the spraying of acomposition without using a propellant. Suitable mechanical spraydevices are, e.g., spray pumps or elastic containers provided with aspray valve, into which the cosmetic composition in accordance withpresent invention is filled under pressure, whereby the elasticcontainer is expanded and wherein the cosmetic composition iscontinuously discharged if the valve is open, due to the contraction ofthe elastic container.

When the hair treatment composition in accordance with present inventionis provided in the form of a hair foam (mousse), the compositioncomprises at least one conventional foaming agent known in the art forthis purpose. The composition is foamed with or without the aid ofpropellants or chemical propellants and the foam may be applied to thehair and may remain in the hair without the need of rinsing the hair. Aproduct in accordance with present invention comprises as additionalcomponent a device for the provision of a foam of the composition.Devices for providing a foam are devices which allow the provision of afoam starting from a liquid, with or without the use of a propellant.Suitable mechanical foaming devices are, e.g., usual foam pumps, orusual aerosol foaming heads.

When the hair treatment composition in accordance with present inventionis provided in the form of a hair gel, it comprises at least one gelforming substance in an amount of preferably from 0.05 to 10, morepreferably from 0.1 to 2 weight %. The viscosity of the gel preferablyamounts to from 100 bis 50,000 mm²/s , more preferably 1,000 bis 15,000mm²/s at 25° C., measured as dynamic viscosity using a Bohlin RheometerCS, measurement body C25 using a shear velocity of 50 s⁻¹.

When the hair treatment composition in accordance with present inventionis provided in the form of a hair wax, it comprises additionallywater-unsoluble fatty substances or waxy substances, or substances whichprovide the composition with a waxy consistence, in an amount ofpreferably 0.5 bis 30 weight %. Suitable water unsoluble substances are,for example, emulgators having a HLB-value of below 7, silicone oils,silicone waxes, wax materials (e.g., waxy alcohols, waxy acids, waxyesters, as well as natural waxes such as beeswax, Carnauba wax, etc.),fatty alcohols, fatty acids, fatty acid esters or high molecularpolyethyleneglycols having a molecular weight of from 800 bis 20,000,preferably from 2,000 to 10,000 g/mol.

When the hair treatment composition in accordance with present inventionis provided in the form of a hair lotion, it is present as asubstantially non-viscous or low viscosity, flowable solution,dispersion or emulsion comprising a content of at least 10 weight %,preferably 20 to 95 weight % of a cosmetically acceptable alcohol. Asalcohols, the usual alcohols used for cosmetic purposes can be named, inparticular the lower C1 to C4 alcohols such as ethanol and isopropanol.

When the hair treatment composition of the present invention is presentin the form of a hair cream, it is preferably provided in the form of anemulsion and it either comprises additional viscosity providingcomponents in an amount of from 0.1 to 10 weight % or the requiredviscosity and creamy consistency is obtained by means of micelleformation using suitable emulsifiers, fatty acids, fatty alcohols,waxes, etc.

In a preferred embodiment the composition in accordance with presentinvention is provided in a form enabling, at the same time, theimpression of a recallable hairdo as well as providing hair coloration.The composition is then formulated as coloring hair treatmentcomposition, e.g., as coloring fixative, coloring cream, coloring foam,etc. It comprises at least one coloring component. The coloringcomponent may be an organic dye, in particular direct dyes or it may bean inorganic pigment.

The total amount of coloring agent amounts in the composition inaccordance with present invention to about 0.01 to 7 weight %,preferably about 0.2 to 4 weight %. Suitable direct colorants to be usedin the composition in accordance with present invention are, e.g.,triphenylmethane colorants, aromatic nitro colorants, azo colorants,quinone colorants, cationic or anionic colorants. Suitable are thefollowing:

Nitro dyes (blue):

1,4-bis[(2-hydroxyethyl)amino]-2-nitrobenzene,1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]-benzene (HCBlue No. 2), 1-amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene(HC Violet No. 1),4-[ethyl-(2-hydroxyethyl)-amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride(HC Blue No. 12),4-[di(2-hydroxyethyl)amino]-1-[(2-methoxy-ethyl)amino]-2-nitrobenzene(HC Blue No. 11),1-[(2,3-di-hydroxypropyl)amino]-4-[methyl-(2-hydroxyethyl)amino]-2-nitrobenzene(HC Blue No. 10),1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride(HC Blue No. 9),1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HCViolet No. 2),1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitro-benzene (HCBlue No. 6), 2-((4-amino-2-nitrophenyl)amino)-5-dimethylamino-benzoicacid (HC Blue No. 13),1-(2-aminoethyl-amino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene,4-(di(2-hydroxyethyl)amino)-2-nitro-1-phenylamino-benzene.

Nitro dyes (red):

1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 7),2-amino-4,6-dinitro-phenene, 1,4-diamino-2-nitrobenzene (CI76070),4-amino-2-nitro-diphenylamine (HC Red No. 1),1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene-hydrochloride (HC RedNo. 13), 1-amino-5-chlor-4-[(2-hydroxyethyl)amino]-2-nitrobenzene,4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3),4-((2-hydroxyethyl)methylamino)-1-(methylamino)-2-nitrobenzene,1-amino-4-((2,3-dihydroxy-propyl)amino)-5-methyl-2-nitrobenzene,1-amino-4-(methylamino)-2-nitrobenzene,4-amino-2-nitro-1-((prop-2-en-1-yl)amino)-benzene,4-amino-3-nitrophenene, 4-[(2-hydroxyethyl)amino]-3-nitrophenene,4-[(2-nitrophenyl)amino]phenene (HC Orange No. 1),1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC OrangeNo. 2),4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HCOrange No. 3),1-amino-5-chlor-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC RedNo. 10), 5-chlor-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HCRed No. 11), 2-[(2-hydroxyethyl)amino -4,6-dinitro-phenene,4-ethylamino-3-nitrobenzoic acid,2-[(4-amino-2-nitrophenyl)amino]-benzoic acid,2-chlor-6-ethylamino-4-nitrophenene, 2-amino-6-chlor-4-nitrophenene,4-[(3-hydroxypropyl)amino]-3-nitrophenene, 2,5-diamino-6-nitropyridine,6-amino-3-((2-hydroxyethyl)amino)-2-nitropyridine,3-amino-6-((2-hydroxyethyl)amino)-2-nitropyridine,3-amino-6-(ethylamino)-2-nitropyridine,3-((2-hydroxyethyl)amino)-6-(methylamino)-2-nitropyridine,3-amino-6-(methylamino)-2-nitropyridine,6-(ethylamino)-3-((2-hydroxyethyl)amino)-2-nitropyridine,1,2,3,4-tetrahydro-6-nitrochinoxaline,7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazin (HC Red No. 14).

Nitro dyes (yellow):

1,2-diamino-4-nitrobenzene (CI76020),1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5),1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC YellowNo. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2),2-(di(2-hydroxyethyl)amino)-5-nitrophenene,2-[(2-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene,2-amino-3-nitrophenene, 1-amino-2-methyl-6-nitrobenzene,1-(2-hydroxy-ethoxy)-3-methylamino-4-nitrobenzene,2,3-(dihydroxypropoxy)-3-methylamino-4-nitrobenzene,2-[(2-hydroxyethyl)amino]-5-nitrophenene (HC Yellow No. 11),3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene-hydrochloride (HCYellow No.9), 1-[(2-Ureidoethyl)amino]-4-nitrobenzene,4-[(2,3-dihydroxypropyl)-amino]-3-nitro-1-trifluormethyl-benzene (HCYellow No. 6), 1-chlor-2,4-bis[(2-hydroxyethyl)amino]-5-nitrobenzene (HCYellow No. 10), 1-amino-4-((2-aminoethyl)amino)-5-methyl-2-nitrobenzene,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-chlor-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12),4-[(2-hydroxyethyl)amino]-3-nitro-1-tri-fluormethyl-benzene (HC YellowNo. 13), 4-[(2-hydroxyethyl)-amino]-3-nitro-benzonitril (HC Yellow No.14), 4-[(2-hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15)3-((2-hydroxyethyl)amino)-4-methyl-1-nitrobenzene,4-chlor-3-((2-hydroxyethyl)amino)-1-nitrobenzene.

Quinone dyes:

1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone,1,4-di[(2-hydroxyethyl)amino]-9,10-anthraquinone (CI61545, Disperse Blue23), 1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone(CI61505, Disperse Blue No. 3),2-[(2-aminoethyl)amino]-9,10-anthraquinone (HC Orange No. 5),1-amino-4-hydroxy-9,10-anthraquinone (CI60710, Disperse Red 15),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone,7-beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracencarboxylicacid (CI75470, Natural Red 4),1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue No.8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8),1,4-diamino-2-methoxy-9,10-anthraquinone (CI62015, Disperse Red No. 11,Solvent Violet No. 26),1,4-dihydroxy-5,8-bis[(2-hydroxyethyl)amino]-9,10-anthraquinone(CI62500, Disperse Blue No. 7, Solvent Blue No. 69),1,4-diamino-9,10-anthraquinone (CI61100, Disperse Violet No. 1),1-amino-4-(methylamino)-9,10-anthraquinone (CI61105, Disperse Violet No.4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone,2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone,N-(6-((3-chlor-4-(methylamino)phenyl)imino)-4-methyl-3-oxo-1,4-cyclohexadien-1-yl)urea(HC Red No. 9),2-((4-(di(2-hydroxyethyl)amino)-phenyl)amino)-5-((2-hydroxyethyl)amino)-2,5-cyclohexadien-1,4-dion(HC Green No. 1), 5-hydroxy-1,4-naphthoquinone (CI75500, Natural BrownNo. 7), 2-hydroxy-1,4-naphthoquinone (CI75480, Natural Orange No. 6),1,2-dihydro-2-(1,3-dihydro-3-oxo-2H-indol-2-yliden)-3H-indol-3-on(CI73000),4-((5-((2-hydroxyethyl)amino-1-methyl-1H-pyrazol-4-yl)imino)-4,5-dihydro-5-((2-hydroxyethyl)imino)-1-methyl-1H-pyrazol-sulfate(1:1),hydrate(1:1)

Basic dyes:

9-(dimethylamino)-benzo[a]phenoxazin-7-ium-chloride (CI51175; Basic BlueNo. 6),di[4-(diethylamino)phenyl][4-(ethyl-amino)naphthyl]carbenium-chloride(CI42595; Basic Blue No. 7),di-(4-(dimethylamino)phenyl)-(4-(methyl-phenylamino)naphthalin-1-yl)carbenium-chloride(CI42563; Basic Blue No. 8),3,7-di(dimethylamino)phenothiazin-5-ium-chloride (CI52015 Basic Blue No.9),di[4-(dimethylamino)phenyl][4-(phenyl-amino)naphthyl]carbenium-chloride(CI44045; Basic Blue No. 26),2-[(4-(ethyl(2-hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium-methylsulfate(CI11154; Basic Blue No. 41),8-amino-2-brom-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalinon-chloride(CI56059; Basic Blue No. 99),bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium-chloride(CI42535; Basic Violet No. 1),Tri(4-amino-3-methylphenyl)carbenium-chloride (CI42520; Basic Violet No.2), Tris[4-(dimethylamino)phenyl]carbenium-chloride (CI42555; BasicViolet No. 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]-benzoicacidchloride (CI45170; Basic Violet No. 10),di(4-aminophenyl)(4-amino-3-methylphenyl)carbeniumchloride (CI42510Basic Violet No. 14),1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzol (CI21010; BasicBrown No. 4),1-[(4-aminophenyl)azo]-7-(tri-methylammonio)-2-naphthol-chloride(CI12250; Basic Brown No. 16),3-[(4-amino-2,5-dimethoxyphenyl)azo]-N,N,N-trimethyl-benzeneaminiumchloride(CI112605, Basic Orange No. 69),1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride,1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chloride(CI12251; Basic Brown No. 17),3,7-diamino-2,8-dimethyl-5-phenylphenazinium-chloride (CI50240; BasicRed No. 2),1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium-chloride(CI11055; Basic Red No. 22),2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)-naphthalin-chloride(CI12245; Basic Red No. 76),2-[2-((2,4-dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-ium-chloride(CI48055; Basic Yellow No. 11),3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)azo]-pyrazol-5-one-chloride(CI12719; Basic Yellow No. 57),di[4-(dimethylamino)phenyl]iminomethan-hydrochloride (CI41000; BasicYellow No. 2),bis[4-(diethylamino)phenyl]phenylcarbenium-hydrogensulfate (1:1)(CI42040; Basic Green No. 1), di(4-(dimethylamino)phenyl)-phenylmethanol(CI42000; Basic Green No. 4),1-(2-morpholiniumpropylamino)-4-hydroxy-9,10-anthraquinone-methylsulfate,1-[(3-(dimethyl-propylaminium)propyl)amino]-4-(methylamino)-9,10-anthraquinone-chloride.

Neutral azo dyes:

1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]-benzene(CI11210, Disperse Red No. 17),1-[di(2-hydroxy-ethyl)amino]-4-[(4-nitrophenyl)azo]-benzene (DisperseBlack No. 9),4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HCYellow No. 7), 2,6-diamino-3-[(pyridin-3-yl)azo]-pyridine,2-((4-(acetylamino)phenyl)azo)-4-methyl-phenene (CI11855; DisperseYellow No. 3).

Acidic dyes:

6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthaline-sulfonic acid-disodiumsalt (CI15985; Food Yellow No. 3; FD&C Yellow No. 6),2,4-dinitro-1-naphthol-7-sulfonic acid-disodium salt (CI10316; AcidYellow No. 1; Food Yellow No. 1),2-(Indan-1,3-dion-2-yl)chinoline-x,x-sulfonic acid (mixture of mono- anddisulfonic acid) (CI47005;D&C Yellow No. 10; Food Yellow No. 13; AcidYellow No. 3),5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazol-3-carboxylicacid-trisodium salt (CI19140; Food Yellow No. 4; Acid Yellow No. 23),9-(2-Carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (CI45350; Acid Yellow No.73; D&C Yellow No. 8), 4-((4-amino-3-sulfo-phenyl)azo)benzenesulfonicacid-disodium salt (CI13015, Acid Yellow No. 9),5-[(2,4-dinitrophenyl)amino]-2-phenylamino-benzenesulfonic acid-sodiumsalt (CI10385; Acid Orange No. 3),4-[(2,4-dihydroxyphenyl)azo]-benzenesulfonic acid monosodium salt(CI14270; Acid Orange No. 6),4-[(2-hydroxynaphth-1-yl)azo]-benzensulfonic acid-sodium salt (CI15510;Acid Orange No. 7),4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo)-phenyl]azo]-benzenesulfonicacid-sodium salt (CI20170; Acid Orange No. 24),4-hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthaline-sulfonicacid-disodium salt (CI14720; Acid Red No. 14),4-hydroxy-3-[(2-methoxyphenyl)azo]-1-naphthaline-sulfonicacid-monosodium salt (CI14710; Acid Red No. 4),6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthaline-disulfonicacid-trisodium salt (CI16255; Ponceau 4R; Acid Red No. 18),3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthaline-disulfonicacid-trisodium salt (CI16185; Acid Red No. 27),8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthaline-disulfonic acid-disodiumsalt (CI17200; Acid Red No. 33),5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthaline-disulfonicacid-disodium salt (CI18065; Acid Red No. 35),2-(3-hydroxy-2,4,5,7-tetraiod-dibenzopyran-6-on-9-yl)-benzoicacid-disodium salt (CI45430; Acid Red No. 51),N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-yliden]-N-ethylethanammonium-hydroxide,internal salt, Sodium salt (CI45100; Acid Red No. 52),8-[(4-(Phenylazo)phenyl)azo]-7-naphthol-1,3-disulfonic acid-disodiumsalt (CI27290; Acid Red No. 73),2′,4′,5′,7′-tetrabrom-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-on-disodiumsalt (CI45380 Acid Red No. 87),2′,4′,5′,7′-tetrabrom-4,5,6,7-tetrachlor-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′[9H]xanthen]-3-on-disodiumsalt (CI45410; Acid Red No. 92),3′,6′-dihydroxy-4′,5′-diiodospiro[isobenzofuran-1(3H),9′(9H)-xanthen]-3-on-disodiumsalt (CI45425; Acid Red No. 95),2-hydroxy-3-((2-hydroxynaphth-1-yl)azo)-5-nitrobenzenesulfonicacid-monosodium salt (CI15685; Acid Red No. 184),(2-sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)phenyl]-carbenium-disodiumsalt betaine (CI42090; Acid Blue No. 9; FD&C Blue No. 1),1,4-bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone-disodium salt(CI 61570; Acid Green No. 25),bis[4-(dimethylamino)phenyl]-(3,7-disulfo-2-hydroxynaphth-1-yl)carbenium-internalsalt monosodium salt (CI44090; Food Green No. 4; Acid Green No. 50),bis[4-(diethylamino)phenyl](2,4-disulfophenyl)carbenium-internal salt,sodium salt (2:1) (CI42045; Food Blue No. 3; Acid Blue No. 1),bis[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium-internalsalt, calcium salt (2:1) (CI42051; Acid Blue No. 3),1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sulfonic acid-sodiumsalt (CI62045; Acid Blue No. 62),1-amino-4-(phenylamino)-9,10-anthraquinone-2-sulfonic acid (CI62055;Acid Blue No. 25),2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-yliden)-2,3-dihydro-3-oxo-1H-indol-5-sulfonicacid-disodium salt (CI73015; Acid Blue No. 74),9-(2-Carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfo-phenyl)amino]xanthylium-internalsalt, monosodium salt (CI45190; Acid Violet No. 9),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone-sodiumsalt (CI60730; D&C Violet No. 2; Acid Violet No. 43),bis[3-nitro-4-[(4-phenylamino)-3-sulfo-phenylamino]-phenyl]-sulfone(CI10410; Acid Brown No. 13),5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthaline-disulfonicacid disodium salt (CI20470; Acid Black No. 1),3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthaline-sulfonicacid-chromium complex (3:2) (CI15711; Acid Black No. 52),3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthaline-sulfonicacid-disodium salt (CI14700; Food Red No. 1; Ponceau SX; FD&C Red No.4),4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-naphthaline-disulfonicacid-tetrasodium salt (CI28440; Food Black No. 1),3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo)-naphthaline-1-sulfonicacid-sodium salt, chromium complex (Acid Red No. 195).

Further colorants known for the purpose of hair coloration, which may becontained in the coloring composition in accordance with the presentinvention are disclosed in E. Sagarin, “Cosmetics, Science andTechnology”, Interscience Publishers Inc., New York (1957), page 503 andonwards, as well as H. Janistyn, “Handbuch der Kosmetika undRiechstoffe”, Volume 3 (1973), page 388 and onwards and K. Schrader,“Grundlagen und Rezepturen der Kosmetika”, 2nd Edition (1989), pages782-815.

Suitable hair coloring pigments are substantially insoluble colorants inthe medium employed in the composition of the present invent ion andthese pigments may be inorganic or organic. Inorganic-organic mixedpigments are also suitable. The pigments are preferably notnanopigments. The preferred particle size is from 1 to 200 μm,preferably 3 to 150 μm, more preferably 10 to 100 μm. Preferred areinorganic pigments. The inorganic pigments may be of natural origin, andmay for example be prepared from chalk, ochre, umbra, green earth, burntterra di sienna or graphite. The pigments may be white pigments, such astitanium dioxide or zinc oxide, they may be black pigments, such as ironoxide black, they may be colored pigments, such as ultra marine or ironoxide red, they may be gloss pigments, metallic effect pigments,pearlescent pigments as well as fluorescent or phosphorescent pigments,although preferably at least one pigment is a colored pigment, i.e. anon-white pigment. Suitable are metal oxides, metal hydroxides and metaloxide hydrates, mixed phase pigments, sulphur containing silicates,metal sulphides, complex metal cyanide s, metal sulphates, metalchromates and metal molybdates as well as the metals themselves (bronzepigments). Suitable are in particular titanium dioxide (CI 77891), blackiron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown ironoxide (CI 77491), manganese violet (CI 77742), ultramarine (sodiumaluminium sulfosilicates, CI 77007, pigment blue 2), chromium oxidehydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), carmine(cochineal). In particular preferred are pigments on the basis of micaor laminated silica minerals which are coated with a metal oxide or ametal oxychloride, such as titanium dioxide or bismuth oxychloride, aswell as additional coloring components, such as iron oxides, iron blue,ultramarine, carmine, etc., where in the color is determined by means ofthe variation of the layer thickness. Such pigments are for example soldunder the trade names Rona®, Colorona®, Dichrona® and Timiron® of theCompany Merck, Germany. Organic pigments are for example the naturalpigments sepia, gummigutt, bone coal, cassel brown, indigo, chlorophylland other plant pigments. Synthetic organic pigments are for example azopigments, anthraquinoid pigments, indigoid pigments, dioxazine pigments,chinacridone pigments, pthalocyanine pigments, isoindolinone pigments,perylene pigments, perinone pigments, metal complex pigments, alkaliblue pigments and diketopyrrolopyrrol pigments.

The hair treatment composition in accordance with the present inventionpreferably comprises additionally at least one hair cosmetic in anamount of from 0.01 to 10, more preferably of from 0.05 to 5 weight %.Preferred hair cosmetics are silicone compounds as well as cationiccompounds, which possess due to cationic groups or groups which can berendered cationic, in particular primary, secondary, tertiary orquaternary amine groups, a substantivity to human hair. Suitablecationic compounds are selected among cationic surfactants, betainic,ampoteric surfactants, cationic polymers, silicone compounds having acationic group or groups which can be rendered cationic, cationicderivatized proteins or protein hydrolyzates and betain.

Suitable silicone compounds are for example polydimethylsiloxane (INCI:Dimethicone), (α-hydro-ω-hydroxypolyoxydimethylsilylene (INCI:Dimethiconol), cyclic dimethylpolysiloxane (INCI: cyclomethicone),trimethyl(octadecyloxy)silane (INCI: stearoxytrimethylsilane),dimethylsiloxane/glycol copolymer (INCI: dimethicone copolyol),dimethylsiloxane/aminoalkylsiloxane copolymer having terminal hydroxygroups (INCI: amodimethicone), monomethylpolysiloxane having lauryl sidechains and terminal polyoxyethylene chains and/or polyoxypropylenechains (INCI: lauryl methicone copolyol), dimethylsiloxane/g lycolcopolymer acetate (INCI: dimethiconcopolyol acetate),dimethylsiloxane/aminoalkylsiloxane copolymer having terminaltrimethylsilyl groups (INCI: trimethylsilylamodimethicone). Preferredsilicone polymers are dimethicone, cyclomethicone and dimethiconole.Mixtures of silicone polymers are also suitable, for example a mixtureof dimethicone and dimethiconol. The designations provided in bracketscorrespond to the nomenclature in accordance with INCI (InternationalCosmetic Ingredients), which is employed for the designation ofcosmetically relative active ingredients and additives.

Usually further known cosmetic additives may be added to the hairtreatment composition in accordance with the present invention, forexample non-fixative non-ionic polymers, such as polyethylene glycols,non-fixative, anionic and natural polymers as well as mixtures thereof,in amounts of preferably from 0.01 to 50 weight %. Perfume oils inamount of from 0.01 to 5 weight %, opacifier such asethyleneglycoldistearate in an amount of from 0.01 to 5 weight %,surfactants or emulsifiers selected from the classes of anionic,cationic, amphoteric or non-ionic surfactants, such as fatty alcoholsulfates, ethoxylated fatty alcohols, fatty acid alcanolamides, such asesters of hydrated fatty acids from rizinus oil, in an amount of from0.1 to 30 weight %, as well as moisturizers, dye receptivity improvingagents, light protective agents, anti-oxidative agents as well aspreservatives in amounts of from 0.01 to 10 weight % may be added.

FIG. 1 shows schematically the method for the provision of a recallable,permanent hairdo. A strand of hair is wound onto a curler (bobbin) and asolution in accordance with the present invention comprising across-linkable macromer is sprayed thereon. By irradiation with asuitable source of energy, for example a UV lamp, the desired permanentshade is fixed. Subsequently the curler is removed.

FIG. 2 shows the deformation of a permanent hairdo and the recovery ofthe permanent shape starting from the temporary shape. The hair curl inthe permanent shape possesses a length l₀. The curl in the deformedshape has a length l₁. The curl in the recovered shape has a length l₂.The degree of re-attaining the permanent shape (recovery) can becalculated as follows: Recovery=(l₁−l₂)/(l₁-l₀).

As measure for the evaluation of the shape memory property of acomposition the memory factor may be employed, which considers thetransformation ability of a permanent hairdo into a temporary shape(shaping factor) as well as the recovery attainability of the permanentform starting from the temporary form (recovery factor, degree ofrecovery). If one starts with the consideration from an even strand ofhair onto which a curly shape has been impressed as permanent shape andonto which, subsequently, a second, even shape has been impressed astemporary shape, the shaping factor can be determined in accordance withthe following criterion: Shaping Degree of evenness factor Strong curlfrom the hairline to the end of hair 0 Lesser degree of curliness fromthe hairline to the 1 end of hair Hairline even, end of hair in the formof a curl 2 Hairline even, slight curvature at the end of hair 3 Evenfrom the end of hairline to the end of hair 4

The recovery factor can be determined in accordance with the followingcriterion: Recovery Degree of recovery of the permanent shape factor  0%0 30% 1 40% 2 50% 3 60% 4 75% 5 100%  6

The memory factor M can be calculated using the shaping factor F, themaximum shaping factor F=4, the recovery factor r and the maximumrecovery factor R=6 in accordance with the following equationM=(f/F)*(r/R)*100

The memory factor should ideally be not below 25, preferably the factorshould be between 25 an d 33.3, more preferred between 37 and 100.

The following examples are intended to illustrate the subject matter ofthe present invention further.

EXAMPLES Example 1 Hair Treatment Using a Thermoset Shape Memory Polymer

A Poly(ε-caprolactone dimethacrylate¹) 2 g THF Ad 100 g¹Prepared in accordance with Example 2 of WO 99/42147

Onto even hair strands having each a length of 19 cm approximately 1 gof the composition are applied. The strands are wound on curlers anddried. Subsequently the strand s are warmed to about 65 to 70° C. and aphotochemical cross-linking reaction is carried out (UV light, Hg-lamp).After cross-linking and cooling to room temperature the curlers areremoved. The curls (impressed permanent shape) had a length of 8 cm.

In order to simulate a deformation by means of cold shaping the curlswere subjected to a load of 25 g and were let to hang at roomtemperature for a) 1 hour, b) 2 hours and 3) 3 hours. The length of thecurls after deformation were a) 10 cm, b) 10 cm and c) 11.2 cm.

After removal of the weights the strands were heated to about 65 to 70°C. The curls retracted spontaneously to lengths of a) 8 cm, b) 8 cm andc) 8.3 cm. This corresponds to a degree of recovery of the impressedhairdo of a) 100%, b) 100% and c) 91%. The degree of recovery (Recovery)can be calculated (see FIG. 2) as follows:Recovery=(1₁−1₂)/(1₁−1₀)

In order to impress a second hairdo (temporary shape) a wavy strand(curl) of a length of 3.2 cm was warmed to 70° C. and stretched to theinitial, complete length of 6.3 cm. Subsequently the strand was cooled.Upon heating to about 65 to 70° C. the curl spontaneously retracted to alength of 3.9 cm. This corresponds to a degree of recovery of theimpressed hairdo (shape) of 77%.

Examples 2 to 31 Hair Treatment Using a Shape Memory Polymer

Compositions were prepared comprising each 2 weight % macromer in amixture of ethanol and water (50/50) employing the following macromersand macromer mixtures in the indicated weight ratios. 2 3 4 5 6 7 8 9PEG(4k)- 100 100 DMA PEG(8k)- 100 100 70 70 80 80 DMA PPG- 30 30 20 20(475)- MA initiator — AiBN — AiBN — AiBN — AiBN 10 11 12 13 14 15 16 17PEG(8k)- 70 70 80 80 70 70 80 80 DMA PEG- 30 30 20 20 (526)-MA PPG- 3030 20 20 (430)-MA initiator — AiBN — AiBN — AiBN — AiBN 18 19 20 21 2223 24 25 PEG(8k)- 70 70 80 80 70 70 80 80 DMA NoO- 30 30 20 20 PPG(400)-MA MeO- 30 30 20 20 PEG(300)- MA initiator — AiBN — AiBN — AiBN — AiBN26 27 28 29 30 31 PEG(8k)- 70 70 80 80 DMA MeO- 30 30 20 20 PPG(200)- MAPEG(10k)- 100 100 DMA Initiator — AiBN — AiBN — AiBN

Application of compositions 2 to 31 was carried out as explained inExample 1. The results obtained were comparable.

Examples 32 to 41 Hair Treatment Using Shape Memory Polymers

Compositions were prepared comprising each 2 weight % macromer in THFusing the following macromers and macromer mixtures in the weight ratiosas indicated: 32 33 34 35 36 37 38 39 40 41 PLGA(7k)-DMA 100 100PCl(10k)-DMA 100 100 70 70 70 70 70 70 NoO-PPG(400)-MA 30 30NoO-PPG(475)-MA 30 30 PEG(526)-MA 30 30 initiator — AiBN — AiBN — AiBN —AiBN — AiBN

The application of compositions 32 to 41 was carried out as disclosed inExample 1. The results obtained were comparable.

Example 42 Hair Treatment Using Shape Memory Polymer

A composition was prepared comprising 2 weight % PLGA(7k)-DMA macromerin ethylacetate and this composition was applied on hair. After the hairhas been brought into the desired shape this shape was fixed by means ofirradiation with UV light.

The preparation of the macromers employed in Examples 2 to 42 wascarried out on the basis of the disclosure in WO 99/42147.

The abbreviations as used in the examples to designate the followingmaterials:

PEG(4k)-DMA, PEG(8k)-DMA, PEG(10k)-DMA:poly(ethylene-glycol)-dimethacrylate

PPG-(475)-MA, PPG-(430)-MA: poly(propylene-glycol)-methacrylate

PEG-(526)-MA poly(ethylene-glycol)-methacrylate

NoO-PPG(400-MA, NoO-PPG(475)-MA:nonyl-poly(propylene-glycol)-methacrylate

MeO-PEG-(300)-MA: methyl-poly(ethylene-glycol)-methacrylate

MeO-PPG(200)-MA: methyl-poly(propylene-glycol)-methacrylate

PLGA(7k)-DMA: poly(L-lactide-co-glycolide)-dimethacrylate

PC1(10k)-DMA: poly(c-caprolactone)-dimethacrylate

Examples 43-50 Hair Treatment Using Thermoplastic Shape Memory Polymers

The shape memory polymers used in the following were prepared from twodifferent macrodiols and trimethylhexan-1,6-diisocyanate in accordancewith the procedure disclosed in example 1 of WO 99/42147. Compositionsfor hair treatment were prepared comprising 0.5 wt. -% of the multiblockcopolymer in a suitable solvent or solvent mixture, such as water,ethanol, tetrahydrofuran, trichloromethane or a mixture ofwater/ethanol/THF. Macrodiol 43 44 45 46 PDX 1500 [wt. %] 48 PLGA 2000[wt. %] 52 PCL 4000 [wt. %] 60 PCL 10000 [wt. %] 50 60 PDL 2000 [wt. %]40 PDL 3000 [wt. %] 50 40 M_(w) Copolymer 79100 150000 130000 115000[g/mol] T_(trans) [° C.] 34 48 55 55 T′_(trans) [° C.] 85 89 87 87Macrodiol 47 48 49 50 PCL 10000 [wt. %] 78 59 40 20 PDL 10000 [wt. %] 2241 60 80 M_(w) Copolymer 208000 357000 282000 300100 [g/mol] T_(trans)[° C.] 55 54 55 54 T′_(trans) [° C.] 91 91 93 94The abbreviations of the macrodiols have the following meaning:PDX: Poly(para-dioxanone)PLGA: Poly(L-lactide-co-glycolide)PCL: Poly(ε-caprolactone)PDL: Poly(pentadecalactone)

The numbers presented in connection with the macrodiols represent theapprox. molecular weight of the macrodiols (±100).

7 g of the composition is applied onto even hair strands. The hair iswound onto curlers, followed by drying. Subsequently the hair is warmedto about 95° C. After cooling to room temperature (about 25° C.) thecurlers are removed. The curls (impressed permanent shape) had a lengthof 4.5 cm. Impressing a second shape of a hairdo (temporary shape) isachieved by warming the curled strand to about 55° C., stretching thehair to the initial full length (16 cm) and cooling to room temperature.Rewarming to about 55° C. gave rise to a spontaneous retraction of thecurls to a length of 8 cm. This corresponds to a degree of recovery ofabout 70%.

1. A method for the treatment of hair, comprising applying a compositiononto hair, wherein the composition comprises at least one active agent,selected among compounds, which are, alone or in combination withfurther compounds, capable, after application to hair and after carryingout hair treatment described in the following, to provide a shape memoryeffect; previously, at the same time or subsequent to the application ofthe composition, bringing the hair into a desired shape (permanentmemory shape) and fixing the memory shape subsequently by inducing achemical or physical change of the applied agents; wherein, after adesired or undesired deformation of the memory shape, the initial memoryshape can be substantially recovered by means of a physical stimulation.2. A method for hair treatment according to claim 1, wherein thecomposition comprises at least one cross-linkable macromer, which formsafter crosslinking a shape-memory polymer, wherein the macromer a)comprises cross-linkable segments, which are cross-linkable by means ofchemical bonds, and b) thermoplastic segments, which are not chemicallycross-linkable, wherein the step of fixing the memory shape is achievedby means of chemical cross-linking of the macromer in order to form theshape-memory polymer, and wherein the shape-memory polymer possesses atleast one transition temperature T_(trans).
 3. A method for hairtreatment, wherein a hairdo (permanent shape) programmed in accordancewith the method according to claim 1 is heated to a temperature aboveT_(trans), the hair is brought into a second (temporary) shape, and thesecond shape is fixed by means of cooling to a temperature belowT_(trans).
 4. A method in accordance with claim 1, wherein thecomposition comprises at least one cross-linkable macromer, which formsafter crosslinking a shape-memory polymer, and wherein thecross-linkable macromer is selected among compounds having the generalformulaA1-(X)_(n)-A2   (I) wherein A1 and A2 represent a reactive, chemicallycross-linkable group and wherein —(X)_(n)— represents a divalent,thermoplastic polymer segment or oligomer segment.
 5. A method accordingto claim 4, wherein the cross-linkable macromer is selected frompolyesters, oligoesters, polyalkylene-glycols, oligoalkylene-glycols,polyalkylene carbonates and oligoalkylene carbonates substituted with atleast two acrylate groups or methacrylate groups.
 6. A method inaccordance with claim 5, wherein the cross-linkable macromer is selectedamong poly(ε-caprolactone)-dimethacrylate,poly(DL-lactide)-dimethacrylate,poly(L-lactide-co-glycolide)-dimethacrylate,poly(ethylene-glycol)dimethacrylate,poly(propylene-glycol)dimethacrylate,PEG-block-PPG-block-PEG-dimethacrylate,poly(ethyleneadipate)-dimethacrylate andhexamethylenecarbonatedimethacrylate.
 7. A method in accordance withclaim 1, wherein the composition comprises in addition a macromer havingonly one chemically reactive group, provided at the terminal or at aside chain.
 8. A method in accordance with claim 7, characterized inthat the additional macromer is selected among compounds of thefollowing general formulaR—(X′)_(n)-A3 wherein R represents a monovalent organic residue, A3represents a reactive, chemically cross-linkable group and wherein—(X′)_(n)— represents a divalent, thermoplastic polymer segment oroligomer segment.
 9. A method in accordance with claim 8, wherein theadditional macromer is selected among polyalkylene-glycols substitutedwith one acrylate group or methacrylate group and monoalkylethersthereof as well as block copolymers thereof.
 10. A method in accordancewith claim 9, wherein the additional macromer substituted with only onechemically reactive group is selected amongpoly(ethylene-glycols)monoacrylate, poly(propylene-glycol)monoacrylateand monalkylethers thereof.
 11. A method in accordance with claim 1,wherein the composition comprises at least two active agents, whichalone show no or only weak shape memory properties, but which, aftercombined application to hair provide a synergistically increased shapememory effect.
 12. A method according to claim 1, wherein thecomposition comprises at least one shape memory polymer, which comprisesa) at least one hard segment which can be crosslinked by means ofphysical interactions, having a first transition temperature T′_(trans),which lies above room temperature, and b) at least one soft segmenthaving a second transition temperature T_(trans) which lies belowT′_(trans), and wherein the memory shape is fixed by means of a physicalcrosslinking of the at least one shape memory polymer.
 13. A methodaccording to claim 12, wherein shaping of the hairs occurs under warmingto a temperature of at least T′_(trans) and wherein subsequent fixationof the hairdo occurs by means of cooling to a temperature belowT′_(trans).
 14. A method for hair treatment, wherein a programmed hairdo(permanent shape) obtained in accordance with a method according toclaim 12, is warmed to a temperature between T′_(trans) and T_(trans),wherein the hair is then brought into a second (temporary) shape andwherein the second shape is fixed by means of cooling to a temperaturebelow T_(trans).
 15. A method for reprogramming of a hairdo (permanentshape) obtained in accordance with the method according to claim 12 intoa new permanent shape, wherein the is hairdo is warmed to a temperatureabove T′_(trans), followed by bringing the hair into a new shape, andfollowed by fixing the new shape by means of cooling to a temperaturebelow T′_(trans).
 16. A method in accordance with claim 12,characterized in that the shape memory polymer possesses a degree ofcrystallinity of from 3 to 80% and wherein the ratio of the moduli ofelasticity below and above T_(trans) is at least
 20. 17. A methodaccording to claim 12, characterized in that the shape memory polymer isa copolyester urethane.
 18. A method according to claim 17,characterized in that the shape memory polymer is a reaction product of(a) two different macrodiols, selected among α,ω-dihydroxypolyesters,α,ω-dihydroxyoligoesters, α,ω-dihydroxypolylactones andα,ω-dihydroxyoligolactones, and (b) at least one diisocyanate.
 19. Amethod for the recovery of a programmed hairdo (permanent shape)obtained by one of the methods according to claim 1, wherein the hairdoin a temporary shape according to claim 3 or in the shape of a hairdoobtained by cold forming, is warmed to a temperature above T_(trans).20. A cosmetic composition, comprising in a cosmetically suitable mediumat least one active agent, selected among compounds which, alone or incombination with other compounds, are capable, after application to hairand carrying out the treatment according to claim 1, to provide a shapememory effect to hairs.
 21. A cosmetic composition according to claim20, wherein the active agent comprises a macromer which iscross-linkable to a shape-memory polymer, wherein the cross-linkedshape-memory polymer possesses at least one transition temperatureT_(trans) and wherein the macromer comprises a) cross-linkable segmentswhich are cross-linkable by means of chemical bonds, and b)thermoplastic segments, which are not chemically cross-linkable.
 22. Acosmetic composition in accordance with claim 20, characterized in thatthe active agent is a shape memory polymer, which comprises at least onehard segment with a first transition temperature T′_(trans), which iscrosslinkable by means of physical interactions, wherein the firsttransition temperature is above room temperature, and at least one softsegment having a second transition temperature T_(trans), which liesbelow T′_(trans).
 23. A composition in accordance with claim 20characterized in that at least two active agents are contained, whichalone do not show shape memory properties or only weak shape memoryproperties but which, after combined application according to claim 1,provide the hair with a synergistically increased shape memory effect.24. A composition in accordance with claim 20, characterized in thatadditionally 0.01 to 25 wt.-% of at least one active agent arecontained, selected among hair cosmetics, hair fixatives and haircolorants.
 25. A cosmetic composition in accordance with claim 20,characterized in that the composition is provided in the form of alotion, a spray lotion, a cream, a gel, a foam gel, an aerosol spray, anon-aerosol spray, an aerosol foam, a non-aerosol foam, a O/W-emulsionor W/O-emulsion, a macro emulsion or a hair wax.
 26. A method oftreating hair comprising the step of applying to the hair macromerswhich are cross-linkable to shape-memory polymers wherein the macromercomprises a) cross-linkable segments, which are cross-linkable by meansof chemical bonds, and b) thermoplastic segments, which are notchemically cross-linkable, wherein the shape-memory polymers do possessat least one transition temperature T_(trans).
 27. A method of treatinghair comprising the step of applying to the hair a physicallycrosslinkable shape memory polymer wherein the shape memory polymercomprises at least one hard segment with a first transition temperatureT′_(trans), which is crosslinkable by means of physical interactions,wherein the first transition temperature is above room temperature, andat least one soft segment having a second transition temperatureT_(trans), which lies below T′_(trans).
 28. A method for the recovery ofa programmed hairdo (permanent shape) obtained by one of the methodsaccording to claim 1, wherein the hairdo in a temporary shape accordingto claim 14 or in the shape of a hairdo obtained by cold forming, iswarmed to a temperature above T_(trans).